Diethyl Oxalate → HCID 55269669, compound

HRID 523349Notes

Reaction equation

HRID 523349 reaction equation
Br[CH:2]1[CH2:7][CH2:6][CH:5]([CH3:8])[CH2:4][CH2:3]1.[Mg].[C:10]([O:17][CH2:18][CH3:19])(=[O:16])[C:11]([O:13]CC)=O.[NH4+].[Cl-]>C1COCC1>[CH3:8][CH:5]1[CH2:6][CH2:7][CH:2]([C:11](=[O:13])[C:10]([O:17][CH2:18][CH3:19])=[O:16])[CH2:3][CH2:4]1

Participants

6

Reactant 4

HCID 7268Diethyl OxalateHCID 22727Cyclohexane, 1-bromo-4-methyl-HCID 25517Ammonium ChlorideHCID 5462224Magnesium

Product 1

HCID 55269669HCID 55269669, compoundYield 76%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

A Grignard reagent prepared from 1-bromo-4-methylcyclohexane (20.0 g, 0.11 mol) and magnesium (2.9 g, 0.12 mol) in THF (110 ml) was added dropwise (during a period of 80 min) to a mechanically stirred solution of diethyl oxalate (16.0 g, 0.11 mol) in THF (250 ml) at −78° C. The mixture was left stirring for 2 h and then slowly warmed up to 0° C. A saturated solution of NH4Cl (100 ml) was added and the formation of a white precipitate was observed. Extraction with diethyl ether (2×), washing with water, drying (Na2SO4) and concentrating afforded 22.6 g of the crude compound. Kugelrohr distillation of 10 g (100° C./2 mbar) gave 7.74 g (76%) of ethyl 2-(4-methylcyclohexyl)-2-oxoacetate as a slightly yellow oil (mixture of cis/trans isomers ca. 1:3).

Workup

  1. waitThe mixture was left
  2. extractionExtraction with diethyl ether (2×)
  3. washwashing with water
  4. dry with materialdrying (Na2SO4)
  5. concentrationconcentrating
  6. customafforded 22.6 g of the crude compound
  7. distillationKugelrohr distillation of 10 g (100° C./2 mbar)

Sources & evidence

ORD record
ord-7da4b458dda94b05af531863fd9432a0
Source dataset
uspto-grants-2016_05
Patent number
US09334464B2

Reaction notes

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